CN110783556A - Composite three-dimensional composite structure film and preparation method and application thereof - Google Patents
Composite three-dimensional composite structure film and preparation method and application thereof Download PDFInfo
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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Abstract
本发明提供了一种三维复合结构的储能薄膜及其制备方法与应用。所述复合型三维结构薄膜的制备方法包括的步骤有：将硅靶材和导电锂离子载体金属靶材在惰性气氛下进行共溅射处理，在基体上生长三维复合型结构薄膜。本发明三维复合型结构薄膜的制备方法生长的三维复合型结构薄膜具有较多的接触界面且界面电阻小的特性，而且形成的界面可以吸收硅材料在在充电时形成的体积膨胀从而导致的在放点时形成的薄膜脱落，减轻周期性体积变化的应力，保持锂离子嵌入/脱出过程中的结构稳定性。另外，所述制备方法有效保证生长的复合型三维结构薄膜电化学性能稳定。
The invention provides a three-dimensional composite structure energy storage film and a preparation method and application thereof. The preparation method of the composite three-dimensional structure film includes the following steps: co-sputtering the silicon target and the conductive lithium ion carrier metal target in an inert atmosphere, and growing the three-dimensional composite structure film on the substrate. The three-dimensional composite structure film grown by the preparation method of the three-dimensional composite structure film of the present invention has the characteristics of more contact interfaces and low interface resistance, and the formed interface can absorb the volume expansion formed by the silicon material during charging, thereby causing The film formed during the discharge point falls off, relieves the stress of periodic volume change, and maintains the structural stability during the lithium ion insertion/extraction process. In addition, the preparation method effectively ensures stable electrochemical performance of the grown composite three-dimensional structure thin film.
Description
技术领域technical field
本发明属于化学电源技术领域，尤其涉及一种三维复合结构薄膜及其制备方法与应用。The invention belongs to the technical field of chemical power sources, and in particular relates to a three-dimensional composite structure film and a preparation method and application thereof.
背景技术Background technique
目前，锂离子电池已得到广泛应用，主要原因是其具有能量密度高、功率密度高、循环性能好、环境友好以及结构多样化等优异特性。在锂离子动力电池的发展需求方面，要求负极材料具有高容量、长寿命、高首效以及快速率充放电等特点。现有的石墨负极材料的理论容量为372mAh/g，其中商业化石墨负极产品已达350mAh/g左右，基本已无提升空间。硅作为锂离子电池负极材料的理论容量可达4200mAh/g左右，且硅在地壳中的含量丰富，仅次于氧，因此成为研究热点。但是硅材料在储锂过程中存在巨大体积效应，约300％，这将导致活性材料膨胀碎裂，从集流体上粉化脱落，失去活性；另外，硅属半导体材料，其导电性较差，电子从硅中迁移至集流体上所需时间较长，致使在大电流充放电时，硅中的电子较难迁移出来，即导致硅负极材料的倍率性能较差。At present, lithium-ion batteries have been widely used, mainly due to their excellent characteristics such as high energy density, high power density, good cycle performance, environmental friendliness, and structural diversification. In terms of the development needs of lithium-ion power batteries, the anode materials are required to have the characteristics of high capacity, long life, high first efficiency, and fast rate charge and discharge. The theoretical capacity of the existing graphite anode material is 372mAh/g, of which the commercial graphite anode product has reached about 350mAh/g, and there is basically no room for improvement. The theoretical capacity of silicon as a negative electrode material for lithium-ion batteries can reach about 4200mAh/g, and the content of silicon in the earth's crust is abundant, second only to oxygen, so it has become a research hotspot. However, silicon materials have a huge volume effect in the process of lithium storage, about 300%, which will cause the active materials to expand and fragment, pulverize and fall off from the current collector, and lose activity; in addition, silicon semiconductor materials have poor conductivity, It takes a long time for electrons to migrate from silicon to the current collector, which makes it difficult for electrons in silicon to migrate out during high current charge and discharge, which results in poor rate performance of silicon anode materials.
硅薄膜在脱嵌锂过程中，体积膨胀主要沿着垂直于薄膜的方向进行，相比于块状硅，可以有效抑制硅的体积效应。硅薄膜的厚度对电极材料的电化学性能影响很大，随着厚度的增加，锂离子的脱嵌过程受抑制，循环性能变差。In the process of lithium deintercalation and intercalation of silicon thin film, the volume expansion is mainly carried out in the direction perpendicular to the thin film, which can effectively suppress the volume effect of silicon compared with bulk silicon. The thickness of the silicon film has a great influence on the electrochemical performance of the electrode material. As the thickness increases, the de-intercalation process of lithium ions is inhibited, and the cycle performance becomes poor.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于克服现有技术的上述不足，提供一种复合型三维复合结构薄膜及其制备方法，以解决现有硅薄膜作为负极材料时几乎采用负载的方式使用而导致其充放电时的体积膨胀，从而导致的薄膜从集流体上脱落的问题。The purpose of the present invention is to overcome the above-mentioned deficiencies of the prior art, and to provide a composite three-dimensional composite structure film and a preparation method thereof, so as to solve the problem that the existing silicon film is almost used as a negative electrode material in a loaded manner, resulting in the charging and discharging of the film. Volume expansion, which leads to the problem of film detachment from the current collector.
本发明的另一目的在于提供一种电极片和电极片的应用，以解决现有含硅的电极片存在如因硅本身为一种半导体材料，其自身的导电性较差等电化学性能不理想的技术问题。Another object of the present invention is to provide an electrode sheet and an application of the electrode sheet, so as to solve the problem that the existing silicon-containing electrode sheet has poor electrochemical performance because silicon itself is a semiconductor material and its own electrical conductivity is poor. Ideal for technical questions.
为了实现本发明的发明目的，本发明的一方面，提供了一种三维复合结构薄膜的制备方法。所述三维复合结构薄膜的制备方法包括如下步骤：In order to achieve the purpose of the present invention, one aspect of the present invention provides a method for preparing a three-dimensional composite structure film. The preparation method of the three-dimensional composite structure film comprises the following steps:
将硅靶材和导电锂离子载体金属靶材在惰性气氛下进行共溅射处理，在基体上生长三维复合结构薄膜。The silicon target and the conductive lithium ion carrier metal target are co-sputtered in an inert atmosphere to grow a three-dimensional composite structure film on the substrate.
本发明的另一方面，提供了一种三维复合结构薄膜。所述三维复合结构薄膜是由本发明三维复合结构薄膜的制备方法生长形成。Another aspect of the present invention provides a three-dimensional composite structure film. The three-dimensional composite structure film is grown and formed by the preparation method of the three-dimensional composite structure film of the present invention.
本发明的又一方面，提供了一种电极片。所述电极片包括集流体，在所述集流体表面上还结合有三维复合结构薄膜，所述三维复合结构薄膜是按照本发明制备方法在所述集流体上生长形成。In yet another aspect of the present invention, an electrode sheet is provided. The electrode sheet includes a current collector, and a three-dimensional composite structure film is combined on the surface of the current collector, and the three-dimensional composite structure film is grown on the current collector according to the preparation method of the present invention.
本发明的再一方面，提供本发明电极片的应用。所述电极片在制备锂离子电池或超级电容器中的应用。Another aspect of the present invention provides the application of the electrode sheet of the present invention. Application of the electrode sheet in the preparation of lithium ion batteries or supercapacitors.
与现有技术相比，本发明三维复合结构薄膜的制备方法将硅靶材和导电锂离子载体金属靶材直接采用射频电源磁控共溅射法沉积形成。这样，使得纳米级导电锂离子载体金属元素与硅形成了三维状结构，从而在三维复合结构薄膜中形成了一个更大的表面积供锂离子容纳，赋予所述三维复合结构膜具有界面电阻小的特性。而且将所述三维复合结构薄膜作为负极膜层后，其所含的导电锂离子载体金属够增加导电性，还有效减少电解液与硅的直接接触，可以减少和阻止电解液与硅之间的不可逆副反应，减少固体电解质膜(SEI)的产生，同时吸收硅在充放电时产生的体积膨胀，减轻周期性体积变化的应力，保持锂离子嵌入/脱出过程中的结构稳定性。另外，采用共溅射法生长形成膜层，其条件易控，有效保证生长的三维复合结构薄膜化学性能稳定，赋予所述三维复合结构薄膜大倍率性能良好，安全性能良好，效率高，适用于工业化大规模的生产。Compared with the prior art, the preparation method of the three-dimensional composite structure film of the present invention directly uses the radio frequency power source magnetron co-sputtering method to deposit and form the silicon target material and the conductive lithium ion carrier metal target material. In this way, the nanoscale conductive lithium ion carrier metal element and silicon form a three-dimensional structure, thereby forming a larger surface area in the three-dimensional composite structure film for lithium ions to accommodate, giving the three-dimensional composite structure film a low interface resistance. characteristic. Moreover, after the three-dimensional composite structure film is used as the negative electrode film layer, the conductive lithium ion carrier metal contained in it can increase the conductivity, and also effectively reduce the direct contact between the electrolyte and silicon, which can reduce and prevent the electrolyte and silicon. Irreversible side reactions reduce the generation of solid electrolyte membrane (SEI), while absorbing the volume expansion of silicon during charging and discharging, reducing the stress of periodic volume changes, and maintaining the structural stability during lithium ion insertion/extraction. In addition, the co-sputtering method is used to grow and form the film layer, and the conditions are easy to control, which effectively ensures the stable chemical properties of the grown three-dimensional composite structure film, and endows the three-dimensional composite structure film with good high-rate performance, good safety performance, and high efficiency, and is suitable for Industrial mass production.
因此，本发明三维复合结构薄膜界面电阻小，其所形成的三维复合结构能够有效阻止电解液与硅的直接接触，可以减少和阻止电解液与硅之间的不可逆副反应，减少固体电解质膜(SEI)的产生，增强导电性，吸收硅充放电时产生的体积膨胀，然后减轻周期性体积变化的应力，同时保持锂离子嵌入/脱出过程中的结构稳定性。Therefore, the interface resistance of the three-dimensional composite structure film of the present invention is small, the three-dimensional composite structure formed by the three-dimensional composite structure can effectively prevent the direct contact between the electrolyte and silicon, can reduce and prevent irreversible side reactions between the electrolyte and silicon, and reduce the solid electrolyte membrane ( The generation of SEI) enhances electrical conductivity, absorbs the volume expansion generated during charging and discharging of silicon, and then relieves the stress of periodic volume changes, while maintaining the structural stability during lithium ion intercalation/extraction.
本发明电极片由于是利用本发明制备方法直接在集流体上生长形成三维复合结构薄膜。因此，所述电极片内阻小，而且所含的三维复合结构薄膜能够有效阻止电解液与硅的直接接触，可以减少和阻止电解液与硅之间的不可逆副反应，减少固体电解质膜(SEI)的产生，增强导电性，吸收硅充放电时产生的体积膨胀，然后减轻周期性体积变化的应力，同时保持锂离子嵌入/脱出过程中的结构稳定性。Because the electrode sheet of the present invention is directly grown on the current collector by the preparation method of the present invention, a three-dimensional composite structure film is formed. Therefore, the internal resistance of the electrode sheet is small, and the three-dimensional composite structure film contained in it can effectively prevent the direct contact between the electrolyte and silicon, reduce and prevent irreversible side reactions between the electrolyte and silicon, and reduce the solid electrolyte membrane (SEI ), enhance the electrical conductivity, absorb the volume expansion of silicon during charging and discharging, and then relieve the stress of the periodic volume change, while maintaining the structural stability during the intercalation/extraction of lithium ions.
由于本发明电极片具有该些优点，含有本发明电极片的锂离子电池的锂离子传导速率高结构稳定性和容量保持率高，赋予所述锂离子电池具有高的首次充放电效率和锂离子电池或超级电容器循环性能好，延长了循环寿命长，安全性能较高。含有本发明电极片的超级电容器内阻小，充放电快速，同时储能性能优异。Due to the advantages of the electrode sheet of the present invention, the lithium ion battery containing the electrode sheet of the present invention has high lithium ion conduction rate and high structural stability and high capacity retention rate, giving the lithium ion battery high initial charge-discharge efficiency and lithium ion The battery or supercapacitor has good cycle performance, prolongs the cycle life, and has high safety performance. The supercapacitor containing the electrode sheet of the present invention has small internal resistance, rapid charge and discharge, and excellent energy storage performance.
附图说明Description of drawings
图1为本发明实施例七与对比例二提供的薄膜电极材料的锂离子电池在150mA/g时的充放电曲线对比图；Fig. 1 is the charge-discharge curve comparison diagram at 150mA/g of the lithium ion battery of the thin-film electrode material provided in Example 7 of the present invention and Comparative Example 2;
图2为本发明实施例七提供的含三维复合结构薄膜电极材料的锂离子电池在150mA/g时首圈、第50圈、第100圈的充放电曲线图；FIG. 2 is a charge-discharge curve diagram of the first cycle, the 50th cycle, and the 100th cycle of the lithium-ion battery containing the three-dimensional composite structure thin-film electrode material provided in the seventh embodiment of the present invention at 150 mA/g;
图3是本发明实施例八、九、十、十一、十二提供的含三维复合结构薄膜电极材料的锂离子电池在150mA/g时首次充放电曲线对比图；其中，曲线1为实施例八得到的锂离子电池的首次充放电曲线，曲线2为实施例九得到的三维复合结构薄膜电极材料的首次充放电曲线，曲线3为实施例十得到的锂离子电池的首次充放电曲线，曲线4为实施例十一得到的锂离子电池的首次充放电曲线1，曲线5为实施例十二得到的锂离子电池的首次充放电曲线；3 is a comparison diagram of the first charge-discharge curves of lithium-ion batteries containing three-dimensional composite structure thin-film electrode materials provided in the eighth, ninth, tenth, eleventh, and twelfth embodiments of the present invention at 150 mA/g; wherein,
图4是本发明实施例七得到的含三维复合结构薄膜电极材料的锂离子电池3000mA/g时的循环性能图；4 is a cycle performance diagram of a lithium ion battery containing a three-dimensional composite structure thin-film electrode material obtained in Example 7 of the present invention at 3000 mA/g;
图5是本发明实施例七得到的含三维复合结构薄膜电极材料锂离子电池3000mA/g时的库伦效率图。FIG. 5 is a Coulomb efficiency diagram of the lithium ion battery containing the three-dimensional composite structure thin film electrode material obtained in Example 7 of the present invention at 3000 mA/g.
具体实施方式Detailed ways
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, but not to limit the present invention.
一方面，本发明实施例提供一种三维复合结构膜的制备方法。所述三维复合结构薄膜的制备方法包括如下步骤：In one aspect, an embodiment of the present invention provides a method for preparing a three-dimensional composite structural film. The preparation method of the three-dimensional composite structure film comprises the following steps:
将硅靶材和导电锂离子载体金属靶材在惰性气氛下进行共溅射处理，在基体上生长三维复合结构薄膜。The silicon target and the conductive lithium ion carrier metal target are co-sputtered in an inert atmosphere to grow a three-dimensional composite structure film on the substrate.
其中，在共溅射过程中，所述导电锂离子载体金属元素实现对硅进行掺杂，从而在基体上生长以硅为主体，以所述导电锂离子载体金属为掺杂元素的膜层，从而使得所述三维复合结构薄膜中形成了一个更大的表面积供锂离子容纳，以显著降低三维复合结构薄膜的界面电阻。同时由于其所形成的三维结构能够有效阻止电解液与硅的直接接触，可以减少和阻止电解液与硅之间的不可逆副反应，减少固体电解质膜(SEI)的产生，增强导电性，同时吸收硅充放电时产生的体积膨胀，然后减轻周期性体积变化的应力，同时保持锂离子嵌入/脱出过程中的结构稳定性。因此，在一实施例中，所述导电锂离子载体金属靶材包括金、银、铝、钴、锰、钼、锡、钒中的至少一种单质靶或合金靶或金、银、铝、钴、锰、钼、锡、钒中的至少一种化合物靶。所述化合物靶可以是氧化铝、氧化银、氧化钴等化合物中的至少一种。在具体实施例中，各靶应该是选用高纯度的靶材，如纯度为99.99％的相应陶瓷靶材。该些导电锂离子载体金属靶材所含的元素具有高导电，允许锂离子通过的特性，能够形成更大的表面积供锂离子容纳，从而显著降低所述三维复合结构薄膜的内阻，而且在三维结构的作用下具有高的电化学反应的稳定性。Wherein, in the co-sputtering process, the conductive lithium ion carrier metal element realizes doping of silicon, so that a film layer with silicon as the main body and the conductive lithium ion carrier metal as the doping element is grown on the substrate, Therefore, a larger surface area is formed in the three-dimensional composite structure film for accommodating lithium ions, so as to significantly reduce the interface resistance of the three-dimensional composite structure film. At the same time, because the three-dimensional structure formed by it can effectively prevent the direct contact between the electrolyte and silicon, it can reduce and prevent irreversible side reactions between the electrolyte and silicon, reduce the generation of solid electrolyte membrane (SEI), enhance conductivity, and absorb The volume expansion of silicon during charging and discharging then relieves the stress of periodic volume changes while maintaining the structural stability during Li-ion intercalation/extraction. Therefore, in one embodiment, the conductive lithium ion carrier metal target material comprises at least one elemental target or alloy target or gold, silver, aluminum, At least one compound target of cobalt, manganese, molybdenum, tin, and vanadium. The compound target may be at least one of compounds such as aluminum oxide, silver oxide, and cobalt oxide. In a specific embodiment, each target should be a high-purity target, such as a corresponding ceramic target with a purity of 99.99%. The elements contained in these conductive lithium ion carrier metal targets have the characteristics of high conductivity, allowing lithium ions to pass through, and can form a larger surface area for lithium ions to accommodate, thereby significantly reducing the internal resistance of the three-dimensional composite structure film. Under the action of three-dimensional structure, it has high stability of electrochemical reaction.
一实施例中，所述共溅射处理的溅射功率满足：溅射所述硅靶材功率与溅射高导电锂离子载体金属靶材的功率比为8:1～1:1。通过控制两靶材的溅射功率比，从而控制三维复合结构薄膜中的高导电锂离子载体金属元素在硅基体中的掺杂含量，也即是间接通过优化高导电锂离子载体金属的掺杂含量从而实现优化三维复合结构薄膜的内阻和相应的电化学性能。In one embodiment, the sputtering power of the co-sputtering process satisfies: the power ratio of the power for sputtering the silicon target to the power for sputtering the highly conductive lithium ion carrier metal target is 8:1 to 1:1. By controlling the sputtering power ratio of the two targets, the doping content of the highly conductive lithium ion carrier metal element in the three-dimensional composite structure film in the silicon matrix is controlled, that is, indirectly by optimizing the doping of the highly conductive lithium ion carrier metal. content to optimize the internal resistance and corresponding electrochemical performance of the three-dimensional composite structure film.
在另一实施例中，在所述共溅射处理过程中，所述基体的温度控制为100℃-800℃。一实施例中，所述惰性气氛也可以称为溅射气氛为氮气、氩气、氨气中的至少一种或多种气体的混合气氛，在进一步实施例中，在所述惰性气氛的气体中还可以混合氧气。在所述惰性气氛中混入氧气，硅在溅射时会有部分硅氧化还原反应成氧化亚硅，形成硅和氧化亚硅的复合薄膜，与导电锂离子载体靶材形成的三维复合结构薄膜性能同样优异。当为两种或两种以上气体时，混合气体的体积比可以根据需要进行调节。其中，氮气、氩气、氧气、氨气可以是99.998％的纯度。基体与靶材之间的间距优选为30-90mm，具体的如50mm。通过控制基体的温度和高纯度的气氛环境，从而保证并提高生长的复合型三维复合结构薄膜的质量，从而保证和提高其电化学性能。In another embodiment, during the co-sputtering process, the temperature of the substrate is controlled to be 100°C-800°C. In an embodiment, the inert atmosphere may also be referred to as a sputtering atmosphere, which is a mixed atmosphere of at least one or more gases selected from nitrogen, argon, and ammonia. In a further embodiment, the gas in the inert atmosphere Oxygen can also be mixed in. When oxygen is mixed into the inert atmosphere, part of the silicon will be redox-reacted into silicon oxide during sputtering, forming a composite film of silicon and silicon oxide, and the three-dimensional composite structure film formed with the conductive lithium ion carrier target. Also excellent. When there are two or more gases, the volume ratio of the mixed gas can be adjusted as required. Among them, nitrogen, argon, oxygen, and ammonia can be 99.998% pure. The distance between the substrate and the target is preferably 30-90 mm, specifically 50 mm. By controlling the temperature of the substrate and the high-purity atmosphere environment, the quality of the grown composite three-dimensional composite structure film is guaranteed and improved, thereby ensuring and improving its electrochemical performance.
另外，在上述所述共溅射处理的条件下，可以控制溅射时间来控制生长三维复合结构薄膜的厚度，如可以但不仅仅为0.1-10μm，具体的如1μm。In addition, under the conditions of the above co-sputtering treatment, the sputtering time can be controlled to control the thickness of the three-dimensional composite structure thin film, such as but not only 0.1-10 μm, specifically 1 μm.
上述制备方法各实施例中的硅靶材可以直接用现成的硅陶瓷靶材。也可以用单晶硅硅片或者硅粉末的压制靶材。The silicon target material in each embodiment of the above preparation method can directly use the ready-made silicon ceramic target material. A single-crystal silicon wafer or a pressed target of silicon powder can also be used.
一实施例中，上述各实施例中的所述基体为化学电源负极集流体。在具体实施例中，所述基体可以是铜箔。In one embodiment, the substrate in each of the above embodiments is a negative current collector of a chemical power source. In a specific embodiment, the substrate may be copper foil.
因此，上文所述三维复合结构薄膜的制备方法将硅靶材和高导电锂离子载体金属靶材直接采用射频磁控共溅射法沉积形成。这样，沉积生长的三维复合结构薄膜是以硅为主体，以纳米级高导电锂离子载体金属元素为掺杂元素掺杂于所述硅为主体中，从而在三维复合结构薄膜中形成了一个更大的表面积供锂离子容纳，赋予所述三维复合结构薄膜具有界面电阻小的特性和可很好的发挥铝、银等高导电锂离子载体的高导电特性。而且该特性三维复合结构薄膜能够有效阻止电解液与硅的直接接触，可以减少和阻止电解液与硅主体之间的不可逆副反应，减少固体电解质膜(SEI)的产生，同时，形成的三维结构还可以吸收硅在充放电时产生的体积膨胀，减轻周期性体积变化的应力，保持锂离子嵌入/脱出过程中的结构稳定性，同时生长的三维复合结构薄膜大倍率性能良好，安全性能良好。而且所述制备方法采用共溅射法生长形成膜层，其条件易控，有效保证生长的三维复合结构薄膜化学性能稳定，效率高，适用于工业化大规模的生产。Therefore, in the preparation method of the three-dimensional composite structure film described above, the silicon target and the highly conductive lithium ion carrier metal target are directly deposited by the radio frequency magnetron co-sputtering method. In this way, the deposited and grown three-dimensional composite structure film is mainly composed of silicon, and the nano-scale highly conductive lithium ion carrier metal element is used as a doping element to dope the silicon as the main body, thereby forming a more complex structure in the three-dimensional composite structure film. The large surface area is used for accommodating lithium ions, which endows the three-dimensional composite structure film with the characteristics of low interface resistance and can well exert the high conductivity properties of highly conductive lithium ion carriers such as aluminum and silver. Moreover, the characteristic three-dimensional composite structure film can effectively prevent the direct contact between the electrolyte and silicon, reduce and prevent irreversible side reactions between the electrolyte and the silicon host, and reduce the generation of solid electrolyte membrane (SEI). At the same time, the three-dimensional structure formed It can also absorb the volume expansion of silicon during charging and discharging, reduce the stress of periodic volume changes, and maintain the structural stability during lithium ion insertion/extraction. At the same time, the grown three-dimensional composite structure film has good high rate performance and good safety performance. Moreover, the preparation method adopts the co-sputtering method to grow the film layer, and its conditions are easy to control, effectively ensuring the chemical properties of the grown three-dimensional composite structure film are stable, and the efficiency is high, and is suitable for industrialized large-scale production.
相应地，基于上文所述三维复合结构薄膜的制备方法，本发明实施例还提供了一种三维复合结构薄膜。由于所述三维复合结构薄膜是由上文所述三维复合结构薄膜的制备方法制备获得，因此，所述三维复合结构薄膜具有如上文所述的特性：界面电阻小，具有良好导电性能；而且所述特性三维复合结构薄膜能够有效阻止电解液与硅主体元素的直接接触，可以减少和阻止电解液与硅主体之间的不可逆副反应，减少固体电解质膜(SEI)的产生，形成的三维结构还可以吸收硅在充放电时产生的体积膨胀，减轻周期性体积变化的应力，保持锂离子嵌入/脱出过程中的结构稳定性，同时生长的三维复合结构薄膜大倍率性能良好，安全性能良好。Correspondingly, based on the above-mentioned preparation method of the three-dimensional composite structure film, an embodiment of the present invention further provides a three-dimensional composite structure film. Since the three-dimensional composite structure film is prepared by the above-mentioned preparation method of the three-dimensional composite structure film, the three-dimensional composite structure film has the above-mentioned characteristics: small interface resistance, good electrical conductivity; The three-dimensional composite structure film with the above-mentioned characteristics can effectively prevent the direct contact between the electrolyte and the silicon host element, can reduce and prevent irreversible side reactions between the electrolyte and the silicon host, and reduce the generation of solid electrolyte membrane (SEI). It can absorb the volume expansion of silicon during charging and discharging, reduce the stress of periodic volume change, and maintain the structural stability during the process of lithium ion insertion/extraction.
另一方面，本发明实施例还提供了一种电极片。电极片包括集流体，在所述集流体表面上还结合有三维复合结构薄膜，所述三维复合结构薄膜是按照上文所述制备方法在所述集流体上生长形成。其中，由于按照上文所述制备方法生长的三维复合结构薄膜，因此，所述集流体优选是负极集流体。如可以但不仅仅是铜箔。生长的所述复合型三维复合结构薄膜可以但不仅仅控制为0.1-10μm，具体的如1μm。因此，所述电极片内阻小，而且所含的三维复合结构薄膜能够有效阻止电解液与纳米级高导电锂离子载体金属元素的直接接触，可以减少和阻止电解液与硅主体之间的不可逆副反应，减少固体电解质膜(SEI)的产生，吸收硅充放电时产生的体积膨胀，然后减轻周期性体积变化的应力，同时保持锂离子嵌入/脱出过程中的结构稳定性。On the other hand, an embodiment of the present invention also provides an electrode sheet. The electrode sheet includes a current collector, and a three-dimensional composite structure film is combined on the surface of the current collector, and the three-dimensional composite structure film is grown on the current collector according to the preparation method described above. Wherein, because of the three-dimensional composite structure film grown according to the above-mentioned preparation method, the current collector is preferably a negative electrode current collector. Such as can but not only copper foil. The grown composite three-dimensional composite structure film can be but not only controlled to be 0.1-10 μm, specifically 1 μm. Therefore, the internal resistance of the electrode sheet is small, and the three-dimensional composite structure film contained in the electrode sheet can effectively prevent the direct contact between the electrolyte and the nano-scale highly conductive lithium ion carrier metal element, and can reduce and prevent the irreversible between the electrolyte and the silicon host. Side reactions, reducing the generation of solid electrolyte membrane (SEI), absorbing the volume expansion of silicon during charging and discharging, and then alleviating the stress of periodic volume changes, while maintaining the structural stability during lithium ion insertion/extraction.
基于本发明实施例所述电极片具有上述该些优点，因此，所述电极片在制备锂离子电池或超级电容器中的应用。当所述电极片在锂离子电池中应用时，所述锂离子电池理所当然的包括必要的组件，如包括由正极、负极和隔膜形成的电芯。其中，所述负极为上文所述电极片。其他组件可以是常规锂离子电池所含的常规组件。这样，所述锂离子电池具有高的首次充放电效率和锂离子电池循环性能好，延长了循环寿命长，安全性能较高。当所述电极片在超级电容器中应用时，所述超级电容器理所当然的包括必要的组件，如电极片，所述电极片为上文所述电极片。这样超级电容器的内阻小，充放电快速，同时储能性能优异循环性能好，延长了循环寿命长，安全性能较高。Based on the above-mentioned advantages of the electrode sheet according to the embodiments of the present invention, the electrode sheet is used in the preparation of lithium ion batteries or supercapacitors. When the electrode sheet is used in a lithium ion battery, the lithium ion battery naturally includes necessary components, such as a battery cell formed by a positive electrode, a negative electrode and a separator. Wherein, the negative electrode is the electrode sheet described above. Other components may be conventional components contained in conventional lithium-ion batteries. In this way, the lithium ion battery has high initial charge-discharge efficiency and good cycle performance of the lithium ion battery, prolongs the cycle life, and has high safety performance. When the electrode sheet is applied in a supercapacitor, the supercapacitor naturally includes necessary components, such as an electrode sheet, and the electrode sheet is the above-mentioned electrode sheet. In this way, the internal resistance of the supercapacitor is small, the charge and discharge are fast, and the energy storage performance is excellent, the cycle performance is good, the cycle life is prolonged, and the safety performance is high.
以下通过多个具体实施例来举例说明本发明实施例三维复合结构薄膜及其制备方法和应用等。The three-dimensional composite structure film and its preparation method and application according to the embodiments of the present invention are illustrated by a plurality of specific embodiments below.
实施例一Example 1
本实施例一提供了三维复合结构薄膜及其制备方法。所述三维复合结构薄膜按照包括如下步骤的方法制备：The first embodiment provides a three-dimensional composite structure film and a preparation method thereof. The three-dimensional composite structure film is prepared according to a method comprising the following steps:
S11：将单晶硅硅片与购买的纯度为99.99％的铝陶瓷靶，作为溅射源，在铜箔上，基片与靶距为50mm，在1.0×10-2毫巴的高纯氩气气氛中，采用Si：Al＝4:1的功率比共溅射法制备厚度为0.1μm的Si-Al复合薄膜；在沉积期间，将基板保持在300℃。S11: A single crystal silicon wafer and a purchased aluminum ceramic target with a purity of 99.99 % are used as the sputtering source. In a gas atmosphere, a Si-Al composite film with a thickness of 0.1 μm was prepared by co-sputtering with a power ratio of Si:Al=4:1; during the deposition, the substrate was kept at 300°C.
实施例二
本实施例一提供了三维复合结构薄膜及其制备方法。所述三维复合结构薄膜按照包括如下步骤的方法制备：The first embodiment provides a three-dimensional composite structure film and a preparation method thereof. The three-dimensional composite structure film is prepared according to a method comprising the following steps:
S11：将(100)晶面的单晶硅硅片与购买的纯度为99.99％的锰陶瓷靶，作为溅射源，在铜箔上，基片与靶距为50mm，在1.0×10-2毫巴的高纯氩气气氛中，采用Si：Mn＝2:1的功率比共溅射法制备厚度为0.8μm的Si-Mn复合薄膜；在沉积期间，将基板保持在400℃。S11: Use a single crystal silicon wafer with a (100) crystal plane and a purchased manganese ceramic target with a purity of 99.99 % as a sputtering source. A Si-Mn composite film with a thickness of 0.8 μm was prepared by co-sputtering with a power ratio of Si:Mn=2:1 in a high-purity argon atmosphere of mbar; during the deposition, the substrate was kept at 400 °C.
实施例三
本实施例一提供了三维复合结构薄膜及其制备方法。所三维复合结构薄膜按照包括如下步骤的方法制备：The first embodiment provides a three-dimensional composite structure film and a preparation method thereof. The three-dimensional composite structure film is prepared according to the method comprising the following steps:
S11：将单晶硅硅片与购买的纯度为99.999％的锡瓷靶，作为溅射源，在铜箔上，基片与靶距为50mm，在1.0×10-2毫巴的高纯氩气气氛中，采用Si：Sn＝6:1的功率比共溅射法制备厚度为0.6μm的Si-Sn合薄膜；在沉积期间，将基板保持在300℃。S11: Use a single crystal silicon wafer and a purchased tin-porcelain target with a purity of 99.999% as the sputtering source, on the copper foil, the distance between the substrate and the target is 50mm, and the high-purity argon at 1.0×10 -2 mbar is used as the sputtering source. In a gas atmosphere, a Si-Sn composite film with a thickness of 0.6 μm was prepared by co-sputtering with a power ratio of Si:Sn=6:1; during the deposition, the substrate was kept at 300°C.
实施例四
本实施例一提供了三维复合结构薄膜及其制备方法。所述三维复合结构薄膜按照包括如下步骤的方法制备：The first embodiment provides a three-dimensional composite structure film and a preparation method thereof. The three-dimensional composite structure film is prepared according to a method comprising the following steps:
S11：将单晶硅硅片与购买的纯度为99.999％的钴陶瓷靶，作为溅射源，在铜箔上，基片与靶距为50mm，在1.0×10-2毫巴的高纯氩气气氛中，采用Si：Co＝8:1的功率比共溅射法制备厚度为0.5μm的Si-Co复合薄膜；在沉积期间，将基板保持在600℃。S11: A single crystal silicon wafer and a purchased cobalt ceramic target with a purity of 99.999 % are used as the sputtering source. In a gas atmosphere, a Si-Co composite film with a thickness of 0.5 μm was prepared by co-sputtering with a power ratio of Si:Co=8:1; during the deposition, the substrate was kept at 600°C.
实施例五
本实施例一提供了三维复合结构薄膜及其制备方法。所三维复合结构薄膜按照包括如下步骤的方法制备：The first embodiment provides a three-dimensional composite structure film and a preparation method thereof. The three-dimensional composite structure film is prepared according to the method comprising the following steps:
S11：将单晶硅硅片与购买的纯度为99.999％的钼陶瓷靶，作为溅射源，在铜箔上，基片与靶距为50mm，在1.0×10-2毫巴的高纯氩气气氛中，采用Si：Mo＝5:1的功率比共溅射法制备厚度为2μm的Si-Mo复合薄膜；在沉积期间，将基板保持在500℃。S11: A single crystal silicon wafer and a purchased molybdenum ceramic target with a purity of 99.999% are used as the sputtering source, on the copper foil, the distance between the substrate and the target is 50mm, and the high-purity argon of 1.0×10 -2 mbar is used as the sputtering source. In a gas atmosphere, Si-Mo composite films with a thickness of 2 μm were prepared by co-sputtering with a power ratio of Si:Mo=5:1; during the deposition, the substrate was kept at 500°C.
实施例六Embodiment 6
本实施例一提供了复三维复合结构薄膜及其制备方法。所述三维复合结构薄膜按照包括如下步骤的方法制备：The first embodiment provides a complex three-dimensional composite structure film and a preparation method thereof. The three-dimensional composite structure film is prepared according to a method comprising the following steps:
S11：将单晶硅硅片与购买的纯度为99.999％的钒陶瓷靶，作为溅射源，在铜箔上，基片与靶距为50mm，在1.0×10-2毫巴的高纯氩气气氛中，采用Si：V＝4:1的功率比共溅射法制备厚度为5μm的Si-V复合薄膜；在沉积期间，将基板保持在700℃。S11: Use a single crystal silicon wafer and a purchased vanadium ceramic target with a purity of 99.999% as a sputtering source, on a copper foil, the distance between the substrate and the target is 50mm, and the high-purity argon at 1.0×10 -2 mbar is used as the sputtering source. In a gas atmosphere, a Si-V composite film with a thickness of 5 μm was prepared by co-sputtering with a power ratio of Si:V=4:1; during the deposition, the substrate was kept at 700°C.
对比例一Comparative Example 1
本实施例一提供了硅薄膜及其制备方法。所述硅薄膜按照包括如下步骤的方法制备：The first embodiment provides a silicon thin film and a preparation method thereof. The silicon film is prepared according to a method comprising the following steps:
S11：将单晶硅硅片作为溅射源，在日本304不锈钢基片上，基质靶距为50mm，在1.0×10-2毫巴的高纯氩气气氛中，溅射制备厚度为0.1μm的Si薄膜；在沉积期间，将基板保持在300℃。S11: Using a single crystal silicon wafer as a sputtering source, on a Japanese 304 stainless steel substrate, the substrate target distance is 50mm, and in a high-purity argon atmosphere of 1.0×10 -2 mbar, sputtering prepares a thickness of 0.1μm. Si thin film; during deposition, the substrate was kept at 300°C.
实施例七至十二和对比例二Embodiment 7 to 12 and comparative example 2
将上述实施例一至实施例六各实施例提供的含有三维复合结构薄膜的铜箔基片作为负极，将对比例一提供的含有三维复合结构薄膜的铜箔作为负极，分别按照如下方法组装成锂离子电池：The copper foil substrate containing the three-dimensional composite structure film provided in the above-mentioned Examples 1 to 6 was used as the negative electrode, and the copper foil containing the three-dimensional composite structure film provided in Comparative Example 1 was used as the negative electrode. Ion battery:
以锂片对薄膜电极，电解液浓度为1mol/L，偏丙烯微孔膜为电池的隔膜，在充满氩气的手套箱中组装成纽扣式电池。A button-type battery was assembled in a glove box filled with argon gas by using a lithium sheet to the thin-film electrode, the electrolyte concentration of 1 mol/L, and the propylene microporous membrane as the battery separator.
各锂离子电池进行如下相关电化学测试条件：充放电电压为0.01V～3V。Each lithium-ion battery was subjected to the following relevant electrochemical test conditions: the charge-discharge voltage was 0.01V to 3V.
各锂离子电池的相关电化学测试结果：The relevant electrochemical test results of each lithium-ion battery:
实施例七提供的锂离子电池在150mA/g的速率时，首次放电比容量为1210mah/g，充电比容量为1198mah/g，如图1所示。而且所述实施例七提供的锂离子电池150mA/g时首圈、第50圈、第100圈的充放电曲线如图2所示。在3000mA/g时的循环性能曲线如图4所示，在3000mA/g时的库伦效率曲线如图5所示。At the rate of 150 mA/g, the lithium-ion battery provided in the seventh embodiment has a specific capacity of first discharge of 1210 mah/g and a specific capacity of charge of 1198 mah/g, as shown in FIG. 1 . Moreover, the charge-discharge curves of the lithium-ion battery provided in the seventh embodiment at 150 mA/g for the first cycle, the 50th cycle, and the 100th cycle are shown in FIG. 2 . The cycle performance curve at 3000 mA/g is shown in FIG. 4 , and the coulomb efficiency curve at 3000 mA/g is shown in FIG. 5 .
实施例八提供的锂离子电池在150mA/g的速率时，首次放电比容量为2916mah/g，放电比容量为3005mah/g。At the rate of 150 mA/g, the lithium ion battery provided in the eighth embodiment has a first discharge specific capacity of 2916mah/g and a discharge specific capacity of 3005mah/g.
实施例九提供的锂离子电池在150mA/g的速率时，首次放电比容量为3237mah/g，放电比容量为3239mah/g。At the rate of 150 mA/g, the lithium ion battery provided in the ninth embodiment has a first discharge specific capacity of 3237mah/g and a discharge specific capacity of 3239mah/g.
实施例十提供的锂离子电池在150mA/g的速率时，首次放电比容量为2855mah/g，放电比容量为2880mah/g。At the rate of 150 mA/g, the lithium ion battery provided in Example 10 has a specific capacity of 2855mah/g for the first discharge and a specific capacity for discharge of 2880mah/g.
实施例十一提供的锂离子电池在150mA/g的速率时，首次放电比容量为2718mah/g，放电比容量为2774mah/g。At the rate of 150 mA/g, the lithium ion battery provided in the eleventh embodiment has a first discharge specific capacity of 2718mah/g and a discharge specific capacity of 2774mah/g.
实施例十二提供的锂离子电池在150mA/g的速率时，首次放电比容量为3071mah/g，放电比容量为3131mah/g。At the rate of 150 mA/g, the lithium ion battery provided in Example 12 has a specific capacity of 3071 mah/g for the first discharge and a specific capacity for discharge of 3131 mah/g.
对比例二提供的锂离子电池在150mA/g的速率时，首次放电比容量为1637mah/g，放电比容量为1684mah/g，如图1所示。At the rate of 150mA/g, the lithium-ion battery provided in Comparative Example 2 has a first discharge specific capacity of 1637mah/g and a discharge specific capacity of 1684mah/g, as shown in Figure 1.
另外，所述实施例八至十二提供的锂离子电池在150mA/g时首次充放电曲线对比曲线如图3所示。In addition, the first charge-discharge curve comparison curve of the lithium-ion batteries provided in the eighth to twelfth embodiments at 150 mA/g is shown in FIG. 3 .
对比实施例七至实施例十二提供的锂离子电池和对比例二提供的锂离子电池充放电性能可知，含有实施例一至六提供的复合型三维复合结构薄膜的锂离子电池明显优于单纯硅负极锂离子电池。因此，各锂离子电池相关电化学测试结果可知，所述锂离子电池具有高的首次充放电效率和良好的循环性能，而且充放电性能稳定。Comparing the charge and discharge performance of the lithium ion batteries provided in Examples 7 to 12 and the lithium ion batteries provided in Comparative Example 2, it can be seen that the lithium ion batteries containing the composite three-dimensional composite structure films provided in Examples 1 to 6 are significantly better than pure silicon Negative Lithium-ion battery. Therefore, according to the relevant electrochemical test results of each lithium-ion battery, the lithium-ion battery has high initial charge-discharge efficiency and good cycle performance, and the charge-discharge performance is stable.
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。The above descriptions are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention shall be included in the protection of the present invention. within the range.
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Application publication date: 20200211 |